Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807058941/sj2403sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807058941/sj2403Isup2.hkl |
CCDC reference: 672778
5,10,15,20-tetrakis(4'-methoxy phenyl)porphyrin, H2T(4-OCH3P)P and its ZnT(4-OCH3P)P complex were synthesized using reported literature methods (Adler et al., 1967, 1970). Crystals of ZnT(4-OCH3P)P complex were grown by vapor diffusion of hexane to the 1,1,2,2-tetrachloroethane solution of the porphyrin over a period of three days.
The C11–C16 benzene ring and its methoxy substituent are disordered over two positions. The disorder components were refined with occupancy factors 0.824 (2) and 0.176 (2) respectively. In addition, the Cl1 atom of the tetrachloroethane solvate also exhibited positional disorder and the occupancies were found to be 0.635 (2) and 0.365 (2) respectively. H atoms were placed in constrained positions with C—H = 0.90–0.98 Å) and refined using a riding model, with Uiso(H) = 1.2 or 1.5 times Ueq(C).
Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004) and SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-32 (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
[Zn(C48H36N4O4)]·C2H2Cl4 | F(000) = 992 |
Mr = 966.01 | Dx = 1.508 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2458 reflections |
a = 14.3347 (3) Å | θ = 2.3–28.3° |
b = 9.6644 (2) Å | µ = 0.88 mm−1 |
c = 15.6369 (3) Å | T = 173 K |
β = 100.865 (1)° | Plate, purple |
V = 2127.44 (7) Å3 | 0.22 × 0.20 × 0.18 mm |
Z = 2 |
Bruker APEXII CCD area-detector diffractometer | 3756 independent reflections |
Radiation source: fine-focus sealed tube | 3427 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
ω and ϕ scans | θmax = 25.0°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −17→16 |
Tmin = 0.830, Tmax = 0.857 | k = −11→11 |
24295 measured reflections | l = −15→18 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0411P)2 + 2.7384P] where P = (Fo2 + 2Fc2)/3 |
3756 reflections | (Δ/σ)max < 0.001 |
362 parameters | Δρmax = 0.85 e Å−3 |
41 restraints | Δρmin = −0.66 e Å−3 |
[Zn(C48H36N4O4)]·C2H2Cl4 | V = 2127.44 (7) Å3 |
Mr = 966.01 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.3347 (3) Å | µ = 0.88 mm−1 |
b = 9.6644 (2) Å | T = 173 K |
c = 15.6369 (3) Å | 0.22 × 0.20 × 0.18 mm |
β = 100.865 (1)° |
Bruker APEXII CCD area-detector diffractometer | 3756 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 3427 reflections with I > 2σ(I) |
Tmin = 0.830, Tmax = 0.857 | Rint = 0.025 |
24295 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 41 restraints |
wR(F2) = 0.093 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.85 e Å−3 |
3756 reflections | Δρmin = −0.66 e Å−3 |
362 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.20385 (17) | 0.0792 (2) | 0.98842 (15) | 0.0204 (5) | |
C2 | 0.23259 (16) | 0.0947 (2) | 1.07868 (15) | 0.0205 (5) | |
C3 | 0.17285 (16) | 0.0793 (2) | 1.13960 (15) | 0.0191 (5) | |
C4 | 0.20165 (17) | 0.0936 (3) | 1.23263 (15) | 0.0223 (5) | |
H4 | 0.2628 | 0.1115 | 1.2628 | 0.027* | |
C5 | 0.12329 (17) | 0.0763 (2) | 1.26797 (15) | 0.0216 (5) | |
H5 | 0.1203 | 0.0821 | 1.3268 | 0.026* | |
C6 | 0.04559 (17) | 0.0472 (2) | 1.19776 (14) | 0.0183 (5) | |
C7 | −0.04665 (18) | 0.0160 (2) | 1.20816 (15) | 0.0198 (5) | |
C8 | −0.12042 (17) | −0.0279 (2) | 1.14119 (15) | 0.0201 (5) | |
C9 | −0.21429 (17) | −0.0649 (3) | 1.15283 (16) | 0.0248 (5) | |
H9 | −0.2361 | −0.0655 | 1.2052 | 0.030* | |
C10 | 0.26482 (18) | 0.0988 (3) | 0.92600 (16) | 0.0258 (5) | |
H10 | 0.3275 | 0.1291 | 0.9379 | 0.031* | |
C11 | 0.33499 (17) | 0.1249 (3) | 1.11235 (15) | 0.0269 (6) | |
C12 | 0.4023 (3) | 0.0244 (6) | 1.0961 (3) | 0.0298 (9) | 0.824 (4) |
H12 | 0.3815 | −0.0552 | 1.0649 | 0.036* | 0.824 (4) |
C13 | 0.4987 (2) | 0.0443 (4) | 1.1265 (2) | 0.0322 (8) | 0.824 (4) |
H13 | 0.5424 | −0.0206 | 1.1145 | 0.039* | 0.824 (4) |
C14 | 0.5297 (2) | 0.1622 (6) | 1.1750 (3) | 0.0290 (8) | 0.824 (4) |
C15 | 0.4647 (4) | 0.2595 (6) | 1.1904 (3) | 0.0270 (10) | 0.824 (4) |
H15 | 0.4857 | 0.3385 | 1.2223 | 0.032* | 0.824 (4) |
C16 | 0.3667 (4) | 0.2413 (6) | 1.1587 (4) | 0.0296 (16) | 0.824 (4) |
H16 | 0.3237 | 0.3083 | 1.1692 | 0.035* | 0.824 (4) |
O1 | 0.62572 (19) | 0.1691 (3) | 1.20344 (19) | 0.0470 (8) | 0.824 (4) |
C23 | 0.6624 (4) | 0.2855 (7) | 1.2535 (4) | 0.0501 (14) | 0.824 (4) |
H23A | 0.7303 | 0.2778 | 1.2692 | 0.075* | 0.824 (4) |
H23B | 0.6357 | 0.2895 | 1.3053 | 0.075* | 0.824 (4) |
H23C | 0.6462 | 0.3682 | 1.2200 | 0.075* | 0.824 (4) |
C12' | 0.4207 (7) | 0.058 (2) | 1.109 (2) | 0.052 (11) | 0.176 (4) |
H12' | 0.4211 | −0.0254 | 1.0802 | 0.063* | 0.176 (4) |
C13' | 0.5058 (11) | 0.118 (2) | 1.1512 (11) | 0.017 (4) | 0.176 (4) |
H13' | 0.5617 | 0.0691 | 1.1525 | 0.021* | 0.176 (4) |
C14' | 0.5118 (14) | 0.249 (2) | 1.1910 (13) | 0.028 (5) | 0.176 (4) |
C15' | 0.4331 (13) | 0.333 (2) | 1.1942 (9) | 0.026 (4) | 0.176 (4) |
H15' | 0.4323 | 0.4217 | 1.2167 | 0.032* | 0.176 (4) |
C16' | 0.3557 (18) | 0.251 (3) | 1.156 (4) | 0.073 (18) | 0.176 (4) |
H16' | 0.2994 | 0.2959 | 1.1603 | 0.088* | 0.176 (4) |
O1' | 0.5969 (10) | 0.3082 (12) | 1.2332 (8) | 0.037 (3) | 0.176 (4) |
C23' | 0.679 (2) | 0.222 (3) | 1.242 (2) | 0.059 (9) | 0.176 (4) |
H23D | 0.7334 | 0.2711 | 1.2721 | 0.089* | 0.176 (4) |
H23E | 0.6892 | 0.1955 | 1.1851 | 0.089* | 0.176 (4) |
H23F | 0.6694 | 0.1401 | 1.2742 | 0.089* | 0.176 (4) |
C17 | −0.07009 (17) | 0.0322 (2) | 1.29712 (15) | 0.0192 (5) | |
C18 | −0.07731 (18) | 0.1626 (3) | 1.33222 (15) | 0.0235 (5) | |
H18 | −0.0643 | 0.2402 | 1.3013 | 0.028* | |
C19 | −0.10368 (18) | 0.1796 (3) | 1.41266 (15) | 0.0238 (5) | |
H19 | −0.1096 | 0.2679 | 1.4347 | 0.029* | |
C20 | −0.12117 (16) | 0.0641 (3) | 1.45993 (14) | 0.0207 (5) | |
C21 | −0.11288 (17) | −0.0672 (3) | 1.42651 (15) | 0.0230 (5) | |
H21 | −0.1242 | −0.1447 | 1.4583 | 0.028* | |
C22 | −0.08777 (17) | −0.0828 (3) | 1.34588 (15) | 0.0230 (5) | |
H22 | −0.0826 | −0.1712 | 1.3238 | 0.028* | |
N1 | 0.07740 (13) | 0.0496 (2) | 1.11961 (12) | 0.0181 (4) | |
N2 | 0.11500 (14) | 0.0388 (2) | 0.94572 (12) | 0.0189 (4) | |
O2 | −0.14729 (13) | 0.06812 (18) | 1.53955 (10) | 0.0260 (4) | |
Zn1 | 0.0000 | 0.0000 | 1.0000 | 0.01790 (13) | |
C24 | −0.1517 (2) | 0.2008 (3) | 1.57856 (17) | 0.0345 (6) | |
H24A | −0.1707 | 0.1903 | 1.6339 | 0.052* | |
H24B | −0.1970 | 0.2576 | 1.5412 | 0.052* | |
H24C | −0.0902 | 0.2437 | 1.5868 | 0.052* | |
C25 | 0.5331 (2) | 0.5607 (4) | 0.01066 (19) | 0.0591 (10) | |
H25 | 0.5176 | 0.6286 | −0.0364 | 0.071* | |
Cl1 | 0.6542 (2) | 0.5167 (3) | 0.0212 (3) | 0.0287 (7) | 0.365 (4) |
Cl1' | 0.6484 (2) | 0.4852 (5) | 0.0185 (3) | 0.1116 (16) | 0.635 (4) |
Cl2 | 0.51877 (7) | 0.64070 (10) | 0.10872 (6) | 0.0602 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0220 (12) | 0.0208 (12) | 0.0196 (11) | 0.0006 (9) | 0.0072 (9) | −0.0011 (9) |
C2 | 0.0206 (12) | 0.0214 (12) | 0.0198 (12) | 0.0012 (9) | 0.0041 (9) | 0.0001 (9) |
C3 | 0.0221 (12) | 0.0183 (11) | 0.0173 (11) | 0.0010 (9) | 0.0044 (9) | −0.0006 (9) |
C4 | 0.0223 (12) | 0.0261 (12) | 0.0172 (11) | −0.0002 (10) | 0.0007 (9) | 0.0013 (9) |
C5 | 0.0287 (13) | 0.0231 (12) | 0.0133 (11) | 0.0010 (10) | 0.0047 (9) | 0.0013 (9) |
C6 | 0.0243 (12) | 0.0161 (11) | 0.0152 (11) | 0.0005 (9) | 0.0052 (9) | 0.0000 (9) |
C7 | 0.0286 (13) | 0.0168 (11) | 0.0155 (11) | 0.0002 (9) | 0.0084 (10) | 0.0006 (9) |
C8 | 0.0250 (12) | 0.0206 (11) | 0.0158 (11) | −0.0003 (9) | 0.0070 (9) | 0.0004 (9) |
C9 | 0.0262 (13) | 0.0320 (14) | 0.0184 (12) | −0.0021 (11) | 0.0101 (10) | −0.0001 (10) |
C10 | 0.0219 (12) | 0.0346 (14) | 0.0222 (12) | −0.0035 (10) | 0.0078 (10) | −0.0012 (10) |
C11 | 0.0223 (13) | 0.0426 (15) | 0.0163 (11) | −0.0027 (11) | 0.0049 (10) | 0.0046 (11) |
C12 | 0.0205 (16) | 0.043 (2) | 0.027 (2) | 0.0000 (19) | 0.0052 (15) | 0.0005 (18) |
C13 | 0.0204 (16) | 0.040 (2) | 0.0372 (19) | 0.0063 (15) | 0.0070 (14) | −0.0082 (17) |
C14 | 0.024 (2) | 0.040 (3) | 0.0238 (18) | −0.003 (2) | 0.0055 (16) | −0.0030 (19) |
C15 | 0.029 (3) | 0.030 (3) | 0.0217 (17) | −0.007 (2) | 0.005 (2) | −0.0040 (16) |
C16 | 0.029 (2) | 0.044 (3) | 0.0154 (19) | −0.0155 (16) | 0.0049 (14) | 0.0014 (15) |
O1 | 0.0206 (14) | 0.0656 (19) | 0.0525 (17) | −0.0016 (13) | 0.0010 (12) | −0.0158 (15) |
C23 | 0.025 (3) | 0.068 (4) | 0.053 (3) | −0.013 (3) | −0.004 (2) | −0.008 (3) |
C12' | 0.052 (11) | 0.053 (11) | 0.052 (11) | −0.0004 (12) | 0.010 (2) | 0.0005 (12) |
C13' | 0.017 (4) | 0.017 (4) | 0.017 (4) | 0.0003 (11) | 0.0033 (14) | −0.0006 (11) |
C14' | 0.025 (12) | 0.035 (13) | 0.024 (9) | −0.004 (12) | 0.008 (10) | −0.006 (8) |
C15' | 0.036 (10) | 0.025 (9) | 0.019 (7) | 0.001 (8) | 0.007 (6) | −0.002 (7) |
C16' | 0.073 (18) | 0.074 (18) | 0.073 (18) | −0.0004 (12) | 0.014 (3) | 0.0002 (12) |
O1' | 0.021 (7) | 0.046 (7) | 0.043 (7) | −0.002 (5) | −0.001 (5) | −0.006 (5) |
C23' | 0.039 (16) | 0.050 (17) | 0.08 (2) | 0.010 (15) | 0.002 (14) | −0.005 (15) |
C17 | 0.0206 (12) | 0.0236 (12) | 0.0142 (11) | −0.0021 (9) | 0.0055 (9) | −0.0004 (9) |
C18 | 0.0309 (13) | 0.0221 (12) | 0.0183 (11) | −0.0042 (10) | 0.0064 (10) | 0.0033 (9) |
C19 | 0.0320 (13) | 0.0203 (12) | 0.0195 (12) | −0.0022 (10) | 0.0057 (10) | −0.0047 (10) |
C20 | 0.0217 (12) | 0.0264 (12) | 0.0144 (11) | −0.0029 (10) | 0.0044 (9) | −0.0011 (9) |
C21 | 0.0308 (13) | 0.0196 (12) | 0.0195 (12) | −0.0047 (10) | 0.0074 (10) | 0.0031 (9) |
C22 | 0.0302 (13) | 0.0193 (12) | 0.0206 (12) | −0.0018 (10) | 0.0077 (10) | −0.0017 (9) |
N1 | 0.0210 (10) | 0.0199 (10) | 0.0143 (9) | −0.0005 (8) | 0.0060 (8) | −0.0009 (8) |
N2 | 0.0209 (10) | 0.0219 (10) | 0.0144 (9) | −0.0007 (8) | 0.0048 (8) | −0.0020 (8) |
O2 | 0.0385 (10) | 0.0268 (9) | 0.0157 (8) | −0.0039 (8) | 0.0126 (7) | −0.0028 (7) |
Zn1 | 0.0195 (2) | 0.0215 (2) | 0.0137 (2) | −0.00120 (14) | 0.00548 (15) | −0.00173 (14) |
C24 | 0.0541 (18) | 0.0313 (15) | 0.0221 (13) | −0.0005 (13) | 0.0173 (12) | −0.0059 (11) |
C25 | 0.088 (3) | 0.057 (2) | 0.0350 (17) | 0.002 (2) | 0.0174 (18) | 0.0028 (16) |
Cl1 | 0.0267 (15) | 0.0282 (11) | 0.0323 (15) | 0.0000 (9) | 0.0084 (11) | 0.0027 (8) |
Cl1' | 0.0485 (16) | 0.205 (4) | 0.082 (2) | 0.0286 (19) | 0.0141 (14) | 0.029 (2) |
Cl2 | 0.0749 (6) | 0.0646 (6) | 0.0448 (5) | −0.0015 (5) | 0.0203 (4) | −0.0157 (4) |
C1—N2 | 1.378 (3) | C12'—C13' | 1.397 (5) |
C1—C2 | 1.402 (3) | C12'—H12' | 0.9300 |
C1—C10 | 1.440 (3) | C13'—C14' | 1.399 (5) |
C2—C3 | 1.404 (3) | C13'—H13' | 0.9300 |
C2—C11 | 1.492 (3) | C14'—O1' | 1.40 (2) |
C3—N1 | 1.375 (3) | C14'—C15' | 1.400 (5) |
C3—C4 | 1.442 (3) | C15'—C16' | 1.400 (5) |
C4—C5 | 1.352 (3) | C15'—H15' | 0.9300 |
C4—H4 | 0.9300 | C16'—H16' | 0.9300 |
C5—C6 | 1.437 (3) | O1'—C23' | 1.43 (3) |
C5—H5 | 0.9300 | C23'—H23D | 0.9600 |
C6—N1 | 1.383 (3) | C23'—H23E | 0.9600 |
C6—C7 | 1.395 (3) | C23'—H23F | 0.9600 |
C7—C8 | 1.406 (3) | C17—C18 | 1.386 (3) |
C7—C17 | 1.500 (3) | C17—C22 | 1.398 (3) |
C8—N2i | 1.380 (3) | C18—C19 | 1.390 (3) |
C8—C9 | 1.437 (3) | C18—H18 | 0.9300 |
C9—C10i | 1.347 (4) | C19—C20 | 1.387 (3) |
C9—H9 | 0.9300 | C19—H19 | 0.9300 |
C10—C9i | 1.347 (4) | C20—O2 | 1.367 (3) |
C10—H10 | 0.9300 | C20—C21 | 1.386 (4) |
C11—C16 | 1.368 (5) | C21—C22 | 1.383 (3) |
C11—C12' | 1.395 (5) | C21—H21 | 0.9300 |
C11—C16' | 1.401 (5) | C22—H22 | 0.9300 |
C11—C12 | 1.426 (5) | N1—Zn1 | 2.0436 (18) |
C12—C13 | 1.387 (6) | N2—C8i | 1.380 (3) |
C12—H12 | 0.9300 | N2—Zn1 | 2.0265 (19) |
C13—C14 | 1.394 (6) | O2—C24 | 1.426 (3) |
C13—H13 | 0.9300 | Zn1—N2i | 2.0264 (19) |
C14—O1 | 1.366 (5) | Zn1—N1i | 2.0436 (18) |
C14—C15 | 1.377 (6) | C24—H24A | 0.9600 |
C15—C16 | 1.410 (7) | C24—H24B | 0.9600 |
C15—H15 | 0.9300 | C24—H24C | 0.9600 |
C16—H16 | 0.9300 | C25—C25ii | 1.507 (7) |
O1—C23 | 1.414 (7) | C25—Cl1 | 1.764 (4) |
C23—H23A | 0.9600 | C25—Cl2 | 1.764 (3) |
C23—H23B | 0.9600 | C25—Cl1' | 1.789 (4) |
C23—H23C | 0.9600 | C25—H25 | 0.9800 |
N2—C1—C2 | 126.0 (2) | C12'—C13'—H13' | 118.1 |
N2—C1—C10 | 109.4 (2) | C14'—C13'—H13' | 118.1 |
C2—C1—C10 | 124.6 (2) | O1'—C14'—C13' | 123.8 (17) |
C1—C2—C3 | 124.8 (2) | O1'—C14'—C15' | 112.4 (15) |
C1—C2—C11 | 117.3 (2) | C13'—C14'—C15' | 123.8 (16) |
C3—C2—C11 | 117.8 (2) | C16'—C15'—C14' | 104 (2) |
N1—C3—C2 | 125.2 (2) | C16'—C15'—H15' | 128.2 |
N1—C3—C4 | 109.4 (2) | C14'—C15'—H15' | 128.2 |
C2—C3—C4 | 125.4 (2) | C15'—C16'—C11 | 141 (2) |
C5—C4—C3 | 107.4 (2) | C15'—C16'—H16' | 109.5 |
C5—C4—H4 | 126.3 | C11—C16'—H16' | 109.5 |
C3—C4—H4 | 126.3 | C14'—O1'—C23' | 115.7 (19) |
C4—C5—C6 | 107.2 (2) | O1'—C23'—H23D | 109.5 |
C4—C5—H5 | 126.4 | O1'—C23'—H23E | 109.5 |
C6—C5—H5 | 126.4 | H23D—C23'—H23E | 109.5 |
N1—C6—C7 | 125.8 (2) | O1'—C23'—H23F | 109.5 |
N1—C6—C5 | 109.6 (2) | H23D—C23'—H23F | 109.5 |
C7—C6—C5 | 124.6 (2) | H23E—C23'—H23F | 109.5 |
C6—C7—C8 | 125.1 (2) | C18—C17—C22 | 118.2 (2) |
C6—C7—C17 | 117.9 (2) | C18—C17—C7 | 120.6 (2) |
C8—C7—C17 | 117.0 (2) | C22—C17—C7 | 121.2 (2) |
N2i—C8—C7 | 125.6 (2) | C17—C18—C19 | 121.3 (2) |
N2i—C8—C9 | 109.5 (2) | C17—C18—H18 | 119.4 |
C7—C8—C9 | 124.9 (2) | C19—C18—H18 | 119.4 |
C10i—C9—C8 | 107.4 (2) | C20—C19—C18 | 119.7 (2) |
C10i—C9—H9 | 126.3 | C20—C19—H19 | 120.2 |
C8—C9—H9 | 126.3 | C18—C19—H19 | 120.2 |
C9i—C10—C1 | 107.3 (2) | O2—C20—C21 | 115.3 (2) |
C9i—C10—H10 | 126.3 | O2—C20—C19 | 124.8 (2) |
C1—C10—H10 | 126.3 | C21—C20—C19 | 119.9 (2) |
C16—C11—C12' | 100.9 (8) | C22—C21—C20 | 119.9 (2) |
C12'—C11—C16' | 108.1 (14) | C22—C21—H21 | 120.0 |
C16—C11—C12 | 119.1 (4) | C20—C21—H21 | 120.0 |
C16'—C11—C12 | 126.2 (12) | C21—C22—C17 | 121.0 (2) |
C16—C11—C2 | 123.7 (4) | C21—C22—H22 | 119.5 |
C12'—C11—C2 | 135.4 (8) | C17—C22—H22 | 119.5 |
C16'—C11—C2 | 116.5 (11) | C3—N1—C6 | 106.40 (18) |
C12—C11—C2 | 117.2 (3) | C3—N1—Zn1 | 127.04 (15) |
C13—C12—C11 | 120.6 (5) | C6—N1—Zn1 | 126.32 (15) |
C13—C12—H12 | 119.7 | C1—N2—C8i | 106.28 (19) |
C11—C12—H12 | 119.7 | C1—N2—Zn1 | 126.86 (15) |
C12—C13—C14 | 119.6 (4) | C8i—N2—Zn1 | 126.85 (16) |
C12—C13—H13 | 120.2 | C20—O2—C24 | 117.18 (19) |
C14—C13—H13 | 120.2 | N2i—Zn1—N2 | 180.0 |
O1—C14—C15 | 125.6 (5) | N2i—Zn1—N1i | 89.75 (8) |
O1—C14—C13 | 114.5 (4) | N2—Zn1—N1i | 90.25 (8) |
C15—C14—C13 | 119.8 (4) | N2i—Zn1—N1 | 90.25 (8) |
C14—C15—C16 | 121.0 (4) | N2—Zn1—N1 | 89.75 (8) |
C14—C15—H15 | 119.5 | N1i—Zn1—N1 | 180.0 |
C16—C15—H15 | 119.5 | O2—C24—H24A | 109.5 |
C11—C16—C15 | 119.9 (5) | O2—C24—H24B | 109.5 |
C11—C16—H16 | 120.0 | H24A—C24—H24B | 109.5 |
C15—C16—H16 | 120.0 | O2—C24—H24C | 109.5 |
C14—O1—C23 | 117.8 (4) | H24A—C24—H24C | 109.5 |
O1—C23—H23A | 109.5 | H24B—C24—H24C | 109.5 |
O1—C23—H23B | 109.5 | C25ii—C25—Cl1 | 113.7 (3) |
H23A—C23—H23B | 109.5 | C25ii—C25—Cl2 | 111.2 (3) |
O1—C23—H23C | 109.5 | Cl1—C25—Cl2 | 107.4 (2) |
H23A—C23—H23C | 109.5 | C25ii—C25—Cl1' | 103.5 (3) |
H23B—C23—H23C | 109.5 | Cl2—C25—Cl1' | 112.1 (2) |
C11—C12'—C13' | 119.3 (13) | C25ii—C25—H25 | 108.1 |
C11—C12'—H12' | 120.4 | Cl1—C25—H25 | 108.1 |
C13'—C12'—H12' | 120.4 | Cl2—C25—H25 | 108.1 |
C12'—C13'—C14' | 123.9 (16) | Cl1'—C25—H25 | 113.6 |
N2—C1—C2—C3 | −4.1 (4) | C12—C11—C12'—C13' | −175 (7) |
C10—C1—C2—C3 | 178.2 (2) | C2—C11—C12'—C13' | −178.8 (13) |
N2—C1—C2—C11 | 173.7 (2) | C11—C12'—C13'—C14' | −5 (4) |
C10—C1—C2—C11 | −3.9 (4) | C12'—C13'—C14'—O1' | 180 (2) |
C1—C2—C3—N1 | −1.3 (4) | C12'—C13'—C14'—C15' | 1 (3) |
C11—C2—C3—N1 | −179.1 (2) | O1'—C14'—C15'—C16' | −175 (3) |
C1—C2—C3—C4 | 179.4 (2) | C13'—C14'—C15'—C16' | 4 (4) |
C11—C2—C3—C4 | 1.5 (4) | C14'—C15'—C16'—C11 | −6 (9) |
N1—C3—C4—C5 | −1.6 (3) | C16—C11—C16'—C15' | 20 (14) |
C2—C3—C4—C5 | 177.8 (2) | C12'—C11—C16'—C15' | 2 (9) |
C3—C4—C5—C6 | 1.6 (3) | C12—C11—C16'—C15' | 3 (10) |
C4—C5—C6—N1 | −1.1 (3) | C2—C11—C16'—C15' | −176 (6) |
C4—C5—C6—C7 | 176.6 (2) | C13'—C14'—O1'—C23' | −6 (3) |
N1—C6—C7—C8 | 4.9 (4) | C15'—C14'—O1'—C23' | 173 (2) |
C5—C6—C7—C8 | −172.4 (2) | C6—C7—C17—C18 | 71.2 (3) |
N1—C6—C7—C17 | −174.2 (2) | C8—C7—C17—C18 | −108.0 (3) |
C5—C6—C7—C17 | 8.6 (3) | C6—C7—C17—C22 | −110.6 (3) |
C6—C7—C8—N2i | −4.2 (4) | C8—C7—C17—C22 | 70.3 (3) |
C17—C7—C8—N2i | 174.8 (2) | C22—C17—C18—C19 | −1.6 (4) |
C6—C7—C8—C9 | 177.5 (2) | C7—C17—C18—C19 | 176.7 (2) |
C17—C7—C8—C9 | −3.4 (4) | C17—C18—C19—C20 | 1.4 (4) |
N2i—C8—C9—C10i | 0.4 (3) | C18—C19—C20—O2 | 179.9 (2) |
C7—C8—C9—C10i | 178.9 (2) | C18—C19—C20—C21 | −0.4 (4) |
N2—C1—C10—C9i | −2.5 (3) | O2—C20—C21—C22 | 179.3 (2) |
C2—C1—C10—C9i | 175.5 (2) | C19—C20—C21—C22 | −0.4 (4) |
C1—C2—C11—C16 | 120.1 (4) | C20—C21—C22—C17 | 0.2 (4) |
C3—C2—C11—C16 | −61.9 (5) | C18—C17—C22—C21 | 0.7 (4) |
C1—C2—C11—C12' | −60 (2) | C7—C17—C22—C21 | −177.5 (2) |
C3—C2—C11—C12' | 118 (2) | C2—C3—N1—C6 | −178.5 (2) |
C1—C2—C11—C16' | 118 (3) | C4—C3—N1—C6 | 1.0 (3) |
C3—C2—C11—C16' | −64 (3) | C2—C3—N1—Zn1 | 6.9 (3) |
C1—C2—C11—C12 | −61.1 (4) | C4—C3—N1—Zn1 | −173.64 (16) |
C3—C2—C11—C12 | 116.9 (3) | C7—C6—N1—C3 | −177.6 (2) |
C16—C11—C12—C13 | −0.2 (6) | C5—C6—N1—C3 | 0.0 (3) |
C12'—C11—C12—C13 | 4 (5) | C7—C6—N1—Zn1 | −2.9 (3) |
C16'—C11—C12—C13 | 2 (3) | C5—C6—N1—Zn1 | 174.68 (15) |
C2—C11—C12—C13 | −179.0 (3) | C2—C1—N2—C8i | −175.8 (2) |
C11—C12—C13—C14 | 1.5 (6) | C10—C1—N2—C8i | 2.2 (3) |
C12—C13—C14—O1 | 178.3 (4) | C2—C1—N2—Zn1 | 3.3 (3) |
C12—C13—C14—C15 | −1.7 (6) | C10—C1—N2—Zn1 | −178.80 (16) |
O1—C14—C15—C16 | −179.3 (5) | C21—C20—O2—C24 | 176.7 (2) |
C13—C14—C15—C16 | 0.7 (6) | C19—C20—O2—C24 | −3.6 (3) |
C12'—C11—C16—C15 | −2.1 (16) | C1—N2—Zn1—N1i | −178.9 (2) |
C16'—C11—C16—C15 | −165 (22) | C8i—N2—Zn1—N1i | 0.0 (2) |
C12—C11—C16—C15 | −0.8 (8) | C1—N2—Zn1—N1 | 1.1 (2) |
C2—C11—C16—C15 | 178.0 (4) | C8i—N2—Zn1—N1 | 180.0 (2) |
C14—C15—C16—C11 | 0.5 (8) | C3—N1—Zn1—N2i | 174.09 (19) |
C15—C14—O1—C23 | 0.3 (6) | C6—N1—Zn1—N2i | 0.53 (19) |
C13—C14—O1—C23 | −179.7 (4) | C3—N1—Zn1—N2 | −5.91 (19) |
C16—C11—C12'—C13' | 1 (3) | C6—N1—Zn1—N2 | −179.47 (19) |
C16'—C11—C12'—C13' | 4 (4) |
Symmetry codes: (i) −x, −y, −z+2; (ii) −x+1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O2iii | 0.93 | 2.51 | 3.273 (2) | 139 (2) |
C22—H22···πiv | 0.93 | 2.58 | 3.436 (2) | 153 |
C25—H25···πv | 0.93 | 2.69 | 3.598 (2) | 153 |
Symmetry codes: (iii) −x, −y, −z+3; (iv) −x, y−1/2, −z+5/2; (v) x, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C48H36N4O4)]·C2H2Cl4 |
Mr | 966.01 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 14.3347 (3), 9.6644 (2), 15.6369 (3) |
β (°) | 100.865 (1) |
V (Å3) | 2127.44 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.88 |
Crystal size (mm) | 0.22 × 0.20 × 0.18 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) |
Tmin, Tmax | 0.830, 0.857 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24295, 3756, 3427 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.093, 1.08 |
No. of reflections | 3756 |
No. of parameters | 362 |
No. of restraints | 41 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.85, −0.66 |
Computer programs: , APEX2 (Bruker, 2004) and SAINT-Plus (Bruker, 2004), SAINT-Plus (Bruker, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-32 (Farrugia, 1997) and Mercury (Macrae et al., 2006).
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O2i | 0.93 | 2.51 | 3.273 (2) | 139 (2) |
C22—H22···πii | 0.93 | 2.58 | 3.436 (2) | 153 |
C25—H25···πiii | 0.93 | 2.69 | 3.598 (2) | 153 |
Symmetry codes: (i) −x, −y, −z+3; (ii) −x, y−1/2, −z+5/2; (iii) x, y, z−1. |
The structural chemistry of porphyrins and metalloporphyrins is of continued interest due to the dramatic changes in the macrocycle stereochemistry that result from varying substituents at the periphery of the porphyrin (Senge, 2000). 5,10,15,20-Tetraphenylporphyrin and its metal complexes crystallize with variety of solvates resulting in the formation of porphyrin sponges (Byrn et al., 1993).
The asymmetric unit of the title compound (I), comprises one half of the porphyrin unit with Zn atom on an inversion centre and one half of the 1,1,2,2,-tetrachloroethane (TCE) solvate, which is also bisected by a centre of inversion (Fig. 1). The ZnII ion is four coordinate and is displaced only slightly (0.0005 (5) Å) from the mean plane of the four N atoms. This is also evident from the average angles for N1—Zn1—N2 (90.0 (6)°) and N1—Zn1—N1 (180.0 (11)°). The average Zn—N bond distance is 2.035 (12) which is similar to that reported for another ZnTPP complex (2.037 (2) Å) (Scheidt et al., 1986). Further, the porphyrin ring of structure (I) showed nearly planar geometry with maximum displacement of core atoms 0.079 (2) Å only. The average ZnII-to-meso-carbon distance 3.45 (4) Å and the average C—C bond distance in the porphyrin ring 1.404 (2) Å are comparable to those reported for the other ZnTPP complex, 3.447 (2) Å and 1.401 (3) Å respectively. The meso aryl groups are almost planar, oriented with an average dihedral angle of 66.9 (2)° relative to the mean plane of the porphyrin ring.
Molecular packing of the complex is stabilized by interesting intermolecular interactions. Fig. 2 shows the two-dimensional network structure formed by C—H···O and C—H···π interactions. The porphyrins shown in gray colour are c-translation equivalents and are interacting with two adjacent neighbors via a pair of C—H···O (C5—H5···O2; H5···O2 = 2.51 Å) hydrogen bonding interactions to form one-dimensional chains parallel to c axis. The porphyrins shown in orange colour are 21 screw equivalents of the gray one-dimensional chains. The angle between nearest neighbour orange and gray coloured porphyrin ring planes is 33.93°. The two one dimensional arrays are linked via C—H···π interactions. The interaction is formed by the H22 of the aryl group centered above the pyrrole (C3–C6/N1) unit of the neighboring porphyrin with a short H22···pyrrole (centroid) distance of 2.576 (2) Å. This is expected for C—H···π interactions (Nishio et al., 1998). The two dimensional network is parallel to the bc plane. Further, these two dimensional networks are linked through solvate mediated C—H···π (C25—H25···C15 (aryl group)) with a H25···C15 distance of 2.695 Å (Fig. 3). This three-dimensional clathrate like structure is formed by interporphyrin and solvate-porphyrin interactions.